Fused tricyclic compounds, process for their preparation, and herbicidal compositions containing them

ABSTRACT

Novel fused tricyclic compounds represented by formula (I) are described. Q, Y, -L-X-, A, A&#39;, B, E, D, n and m are as defined in the disclosure. Also described are the processes for the manufacture of these compounds and agriculturally suitable compositions containing these as active ingredients which are useful as herbicides for general or selective pre-emergent or post-emergent control of undesired plant species.

CROSS REFERENCE TO RELATED APPLICATION

This is a U.S. National Stage Application filed under 35 U.S.C. § 371 ofInternational Application No. PCT/US00/08745 filed Apr. 21, 2000, whichis a Continuation-in-part of U.S. application Ser. No. 09/323,823 filedJun. 2, 1999, and the complete disclosures of which are incorporatedinto this application by reference.

The present invention relates to fused tricyclic compounds, process fortheir preparation, and herbicidal compositions containing them.

BACKGROUND OF THE INVENTION

It is known that some benzoxazine type compounds show herbicidalactivity. They are described in U.S. Pat. No. 4,734,124, 4,761,174,5,084,084 or 5,281,571, European Patent publication No. 0170191 orGerman Patent publication No. 3927438. Certain fused tricyclic compoundswith herbicidal activity were described in European Patent publicationNo. 406993.

However, it is not known that benzoxazine type compounds with afunctional group introduced at position 5 followed by cyclization affordfused tricyclic compounds which exhibit herbicidal activity.

SUMMARY OF THE INVENTION

This invention delineates a method for the control of undesiredvegetation in a plantation crop by the application to the locus of thecrop an effective amount of a compound described herein. The herbicidalcompounds of the present invention are described by the followingformula (I) or its salt:

wherein Q is a heterocycle selected from the group consisting of Q1 toQ24:

wherein R₁ is hydrogen, alkyl, haloalkyl, alkenyl, alkynyl, amino,alkoxyalkyl, acetyl, alkoxycarbonylamino, alkylcarbonylamino oralkoxycarbonyl;

R₂ is alkyl, haloalkyl, alkoxy, haloalkoxy or unsubstituted orsubstituted phenyl;

R₃ is hydrogen, halogen, nitro, amino, alkylamino, haloalkylamino, cyanoor amide;

R4 and R₅ are independently oxygen, sulfur or imino;

Q6, Q7, Q10, Q16 or Q17 may be unsaturated containing one or two doublebonds in the 6-membered ring;

Y is hydrogen or halogen;

—L—X— is —O—, —S—, —S(O)—, —S(O)₂— —CR₆R₇—, —CR₆R₇—O—, —O—CR₆R₇—,—CR₆R₇—S—, S—CR₆R₇—, —CR₆R₇—S(O)—, —S(O)—CR₆R₇, —CR₆R₇—S(O)₂—,—S(O)₂—CR₆R₇—, —CR₆R₇—CR₆R₇—, —CR₆═CR—, —NR₆—, —CR₆═N—, —N═CR₆—, —N═N—,—CR₆R₇—NR₆— or —NR₆—CR₆R₇—;

A is —O—, —S—, —S(O)—, S(O)₂, —NH—, —C(O)—, —C(S)—, —C(NH)— or —CR₆R₇—;

A′ is —O—, —S—, —S(O)—, S(O)₂, —NH—, —C(O)—, —C(S)—, —C(NH)— or—CR₁₀R₁₁—;

n is an integer of 0 to 2;

m is an integer of 0 to 2;

B is N, CH, C, or N⁺

E is a bond, —O—, —S—, —S(O)—, —S(O)₂—, —NH—, —C(O)—, —C(S)—, —C(NH)—,—CR₁₂R₁₃—, —CR₁₂R₁₃—CR₁₂R₁₃—, —CR₁₂═CR₁₃—, ═CR₁₂— or —NR₁₂—;

D is —NR—, —N═CR₁₄—, —O—, —S—, —S(O)—, —S(O)₂—, —CR₁₄R₁₅— or—CR₁₄═CR₁₅—;

R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄ and R₁₅ are independentlyhydrogen, halogen, hydroxy, cyano, nitro, amino, alkyl, alkenyl,alkynyl, cycloalkyl, phenyl, benzyl, aryl, heteroaryl, alkoxy,haloalkoxy, aryloxy, heteroaryloxy, alkylcarbonyl, arylcarbonyl,alkoxycarbonyl, aryloxycarbonyl, amninocarbonylamino,alkylaminocarbonylamino, arylaminocarbonylamino, alkoxyalkyl,alkylthioalkyl, alkoxycarbonylalkyl, cycloalkoxycarbonylalkyl,alkylcarbonyloxyalkyl, alkylcarbonylaminoalkyl,alkoxyalkylcarbonylalkyl, heterocycloalkyl, alkylsulfonyl, arylsulfonyl,alkenylcarbonyl, alkynylcarbonyl, cycloalkylcarbonyl,heteroarylcarbonyl, alkylthiocarbonyl, cycloalkyloxycarbonyl,arylthio-carbonyl, aryl-thiocarbonyl, heteroaryloxycarbonyl,aminocarbonyl, alkylaminocarbonyl, arylaminocarbonyl,heteroarylaminocarbonyl, alkoxycarbonylcarbonyl or arylcarbonylcarbonylwhere any of these groups may be substituted with at least onesubstituent selected from the group consisting of halogen, cyano, nitro,amino, dialkylamino, hydroxyl, carboxyl, alkyl, alkenyl, alkynyl,cycloalkyl, alkylcarbonyl, alkylcarbonyloxy, alkoxy, alkoxycarbonyl,alkylthio, alkylthiocarbonyl, alkoxythiocarbonyl alkylaminocarbonyl,arylaminocarbonyl, alkylsulfonyl, alkenyloxycarbonyl,alkynyloxycarbonyl, aryl, arylcarbonyl, aryloxy, aryloxycarbonyl,arylthio, heteroaryl, heteroaryloxycarbonyl and methylenedioxy, whereinthe alkyl moiety or aryl moiety may be substituted with at least onesubstituent selected from the group consisting of halogen, cyano, nitro,alkyl, alkoxy, haloalkyl, haloalkoxy, alkoxycarbonyl, cycloalkyl, aryland heterocycloalkyl;

R is hydrogen, alkyl alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl,alkoxyalkyl, alkoxyalkoxyalkyl, alkylcarbonyl, arylcarbonyl,alkoxycarbonyl, aryloxycarbonyl, alkoxycarbonylalkyl,alkoxyalkoxycarbonylalkyl, cycloalkoxycarbonylalkyl, aralkyl,heteroaralkyl, aryloxyalkyl or heteroaryloxyalkyl where any of thesegroups may be substituted with at least one substituent selected fromthe group consisting of halogen, cyano, nitro, amino, carboxyl,alkylthioalkyl, hydroxyalkyl, CON(R₁₆)R₁₇ and COON(R₁₆)R₁₇;

R₁₆ and R₁₇ are independently hydrogen, halogen, alkyl, alkenyl,alkynyl, cycloalkyl, alkoxyalkyl, alkylthioalkyl, alkoxycarbonylalkyl,cycloalkoxycarbonylalkyl, alkylcarbonyloxyalkyl,alkylcarbonylaminoalkyl, alkoxyalkylcarbonylalkyl, phenyl or benzylwhere any of these groups may be substituted with at least onesubstituent selected from the group consisting of halogen, cyano,carboxyl, hydroxy, nitro and amino.

DETAILED DESCRIPTION OF THE INVENTION

In the above definitions, the term alkyl used either alone or incompound words such as haloalkyl or alkoxy indicates either straightchain or branched alkyls containing 1-8 carbon atoms. Alkenyl andalkynyl include straight chain or branched alkenes and alkynesrespectively containing 2-8 carbon atoms. The term halogen either aloneor in the compound words such as haloalkyl indicates fluorine, chlorine,bromine, or iodine. Further a haloalkyl is represented by an alkylpartially or fully substituted with halogen atoms that may be same ordifferent. A cycloalkyl group implies a saturated or unsaturatedcarbocycle containing 3-8 carbon atoms. A heterocycloalkyl group is acycloalkyl group carrying 1-4 heteroatoms which are represented byoxygen, nitrogen, or sulfur atoms. An aryl group signifies an aromaticcarbocycle containing 4-10 carbon atoms. A heteroaryl group is anaromatic ring containing 1-4 heteroatoms which are represented byoxygen, nitrogen, or sulfur atoms, and may for example be furanyl,pyridyl, thienyl, pyrimidinyl, benzofuranyl, quinolyl, benzothienyl orquinoxalyl.

The compound of the formula (I) may form a salt with an acidic substanceor a basic substance. The salt with an acidic substance may be aninorganic acid salt such as a hydrochloride, a hydrobromide, aphosphate, a sulfate or a nitrate. The salt with a basic substance maybe a salt of an inorganic or organic base such as a sodium salt, apotassium salt, a calcium salt, a quaternary ammonium salt such asammonium salt or a dimethylamine salt.

The compound of the formula (I) may exist as geometrical or opticalisomers and the present invention includes all of these isomeric forms.

Preferred compounds for the reasons of ease of synthesis or greaterherbicidal efficacy are represented by the formula (I) wherein; (1) theformula (I) is

Wherein Q, R, R₆, R₇, R₁₂, R₁₃ and Y are the same as defined above;

(2) Q is Q1-5, Q16 or Q17;

(3) Y is fluorine;

More preferred is a compound of the formula (I-1)

Wherein Q is Q1 or Q3; Y is fluorine; and R, R₆, R₇, R₁₂ and R₁₃ are thesame as defined above.

Specific examples of preferred compounds are as follows:

8-[1-Methyl-6-(trifluoromethyl)-2,4-(1H,3H)-pyrimidinedione-3-yl]-9-fluoro-5H-pyrazino[1,2,3-de]-1,4-benzoxazine-3,6-(2H,7H)dione (1-1),8-[4-Chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-9-fluoro-5H-pyrazino[1,2,3-de]-1,4-benzoxazine-3,6(2H,7H)-dione (1-13),8-[4-Chloro-5-(difluoromethoxy)-1-methyl-1H-pyrazole-3-yl)-9-fluoro-5H-pyrazino[1,2,3-de]-1,4-benzoxazine-3,6(2H,7H)-dione (1-25),9-Flouro-8-(4,5,6,7-tetrahydro-2H-isoindole-1,3-dione-2-yl)-5H-pyrazino[1,2,3de]-1,4-benzoxazine-3,6(2H,7H)-dione (1-37),8-[4-Chloro-1-methyl-5-trifluoromethyl)-1H-pyrazol-3-yl]-]-9-fluoro-2-R-methyl-5H-pyrazino[1,2,3-de-1,4-benzoxazine-3,6(2,7H)-dione (1-48),8-[4-Chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-2,2-dimethyl-9-fluoro-5H-pyrazino[1,2,3-de]-1,4-benzoxazine-3,6(2H,7H)-dione (1-52) and8-[-4-Chloro-5-(difluoromethoxy)-1-methyl-1H-pyrazol-3-yl)-9-fluoro-2-R-methyl-5H-pyrazino[1,2,3-de]-1,4-benzoxazine-3,6(2H,7H)-dione (1-55).

The compound of the formula (I) can be produced, for example, by thefollowing methods A to D:

In the above formulas, Q, R, —L—X—, Y, n, R₆, R₇, R₁₂, R₁₃ and A are thesame as defined previously.

The reactive derivative of R₁₂(R₁₃)C(Cl)COOH may, for example, be acompound selected from the group consisting of an alkyl halide, alkylacid halide, aryl acid halide, alkyl acid anhydride, aryl acidanhydride, alkylhaloformate, alkyl isocyanate, aryl isocyanate, alkyldihalide, aliphatic aldehyde, aliphatic ketone, aromatic aldehyde, andaromatic ketone.

The reaction is conducted usually in the presence of a solvent, ifnecessary, in the presence of a base. The solvent may, for example, bean aromatic hydrocarbon such as benzene or toluene: an ether such asdiethyl ether, tetrahydrofuran or dioxane; a halogenated hydrocarbonsuch as methylene chloride or chloroform; an aprotic polar solvent suchas acetonitrile, dimethylformamide or pyridine. The base may, forexample, be a tertiary amine such as trimethylamine, triethylamine; apyridine; an alkali metal hydroxide such as sodium hydroxide orpotassium hydroxide; an alkali metal carbonate such as sodium carbonateor potassium carbonate; or an alkali metal alkoxide such as sodiummethoxide or sodium ethoxide.

The reaction temperature is usually from 50° to +150° C., preferablyfrom 0° to 100° C. The reaction time is form 0.1 to 24 hours.

The cyclization reaction is carried out usually in a solvent underanhydrous conditions in the presence of a base. The solvent may, forexample, be an aromatic hydrocarbon such as benzene or toluene; an ethersuch as diethyl ether, tetrahydrofuran or dioxane; a halogenatedhydrocarbon such as methylene chloride or chloroform; an aprotic polarsolvent such as acetonitrile, dimethylformamide or pyridine. The basemay, for example, be a tertiary amine such as trimethylamine,triethylamine, N,N-diisopropylethylamine; a pyridine; an alkali metalhydroxide such as sodium hydroxide or potassium hydroxide; an alkalimetal carbonate such as sodium carbonate or potassium carbonate; analkali metal alkoxide such as sodium methoxide or sodium ethoxide, or analkali metal hydride such as sodium hydride or potassium hydride. Alkalimetal halides such as sodium iodide, potassium iodide may be used ascatalysts.

In the above formulas, Q, R, A, —L—X—, Y, R₁₂, R₁₃ and n are the same asdefined above.

In the above formulas, Q, A, A′, B, E, D, —L—X—, Y, n and m are the sameas defined above.

The above nitration reaction is carried out in nitric acid or fumingnitric acid which may be mixed with sulfuric acid or acetic acid. Theamount of nitric acid is usually from 1 to 100 moles per one mole of thecompound of the formula (VIII).

The reaction temperature is usually from 0° to 100° C. The reaction timeis form 0.1 to 24 hours.

The above reduction reaction is carried out by treatment with iron inacetic acid or ethanolic hydrochloric acid, or by hydrogenation usingpalladium on carbon or platinum oxide as catalyst.

The reaction temperature is usually from 0° to 50° C. The reaction timeis from 0.1 to 24 hours.

In the above formulas, Q, A, A′, B, E, D, —L—X—, Y, n and m are the sameas defined above.

The reaction for the formation of X from XI is carried out in a solventsuch as dimethylsulfoxide, tetrahydrofuran, or dioxane in the presenceof a base such as hydrazine. The reaction temperature is usually from 0°to 100° C. The reaction time is from 0.1 to 24 hours.

Now, the present invention will be described with reference to Examples.However, it should be understood that the present invention is by nomeans restricted by these specific Examples.

EXAMPLE 1 Preparation of5-(2-Chloroacetylamino)-6-[4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-7-fluoro-2H-1,4-benzoxazine-3(4H)-one.

4-Chloro-3-[7-fluoro-5-amino-2H-1,4-benzoxazine-3(4H)-on-6-yl]-1-methyl-5-trifluoromethyl-1H-pyrazole(400 mg, 1.10 mmol) was dissolved in anhydrous dioxane and chloroacetylchloride (139.5 mg, 1.20 mmol) was added. Solution was heated to refluxfor 2 hr and solvent removed in vacuo. The residue was washed with etherto afford the title compound (410 mg, 0.93 mmol).

EXAMPLE 2 Preparation of8-[4-Chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-9-fluoro-5H-pyrazino[1,2,3-de]-1,4-benzoxazine-3,6(2H,7H)-dione (Compound No. 1-13).

4-Chloro-3-[7-fluoro-5-(2-chloroacetylamino)-2H-1,4-benzoxazine-3(4H)-on-6-yl]-1-methyl-5-trifluoroznethyl-1H-pyrazole (250 mg, 0.57 mmol) wasdissolved in anhydrous dimethylformamide (10 ml) and solution stirredunder ice-cooling. Sodium hydride (16.4 mg, 95%, 0.65 mmol) was slowlyadded in portions and solution allowed to stir at ambient temperaturefor 2 hr. Solution was then added to ice-water and product extractedwith ethyl acetate. Product was purified by flash chromatography onsilica gel with hexane ethyl acetate (6:4) as eluent (130.4 mg, 0.32mmol); MS ESI (negative ion) 403 (M-1)⁻.

EXAMPLE 3 Preparation of4-chloro-3-[7-fluoro-5-(2-chloropropionylamino)-2H-1,4-benzoxazine-3(4H)-on-6-yl]-1-methyl-5-difluoromethoxy-1H-pyrazole.

4-Chloro-3-[7-fluoro-5-amino-2H-1,4-benzoxazine-3(4H)-on-yl]-1-methyl-5-difluoromethoxy-1H-pyrazole(400 mg, 1.10mmol) was dissolved anhydrous dioxane (10 ml) and2-chloropropionyl chloride (158.4 mg, 97%, 1.21 mmol) was added.Solution was heated to reflux for 2 hr and solvent evaporated in vacuo.The residue was washed with ether to furnish the title compound (408.3mg, 0.90 mmol).

EXAMPLE 4 Preparation of8-[4-Chloro-5-(difluoromethoxy)-1-methyl-1H-pyrazole-3-yl)-9-fluoro-5-methyl-5H-pyrazino[1,2,3-de]-1,4-benzoxazine-3,6(2H,7H)-dione (Compound No. 1-26).

4-Chloro-3-[7-fluoro-5-(2-chloropropionylamino)-2H-1,4-benzoxazine-3(4H)-on-6yl]-1-methyl-5-difluoromethoxy-1H-pyrazole(300 mg, 0.66 mmol) was dissolved in anhydrous dimethylformamide (10 ml)and solution stirred under ice-cooling. Sodium hydride (20 mg, 95%, 0.79mmol) was added slowly in portions and solution stirred at roomtemperature for 2 hr. Solution was then added to ice-water and productextracted with ethyl acetate. Evaporation of the solvent afforded aresidue which was purified by flash chromatography on silica gel inhexane-ethyl acetate (1:1) to furnish the title compound (209.2 mg, 0.50mmol).

EXAMPLE 5 Preparation of3-[5-(2-chloroacetylamino)-7-fluoro-2H-1,4-benzoxazine-3(4H)-on-6-yl]-1-methyl-6-trifluoromethyl-2,4-(1H,3H)-pyrimidinedione.

3-[5-Amino-7-fluoro-2H-1,4-benzoxazine-3(4H)-on-6-yl]-1-methyl-6-trifluoromethyl-2,4-(1H,3H)-pyrimidinedione(400 mg, 1.07 mmol) was dissolved in anhydrous dioxane and chloroacetylchloride (135.6 mg, 1.20 mmol) was added. Solution was heated to refluxfor 2 hr and solvent removed in vacuo. The residue was washed with etherto afford the title compound (351.9 mg, 0.78 mmol).

EXAMPLE 6 Preparation of 8-[1-methyl-6-(trifluoromethyl)-2,4-(1H,3H)-pyrimidinedione-3-yl]-9-fluoro-5H-pyrazino[1,2,3-de]-1,4-benzoxazine-3,6-(2H,7H)-dione (1-1).

3-[5-(2-Chloroacetylamino)-7-fluoro-2H-1,4-benzoxazine-3(4H)-on-6-yl]-1-methyl-6-trifluoromethyl-2,4-(1H,3H)-pyrimidinedione(271 mg, 0.60 mmol was dissolved in anhydrous acetonitrile (10 ml) andpotassium iodide (14 mg, 0.08 mmol) and N,N-diisopropylethylamine (100.8mg, 0.78 mmol) were added. Solution was refluxed for 2 hr. added towater and extracted with ethyl acetate. Product was purified by flashchromatography on silica gel with hexane-ethyl acetate (1:1) as eluent(218.6 mg, 0.53 mmol).

EXAMPLE 7 Preparation ofMethyl-2-R-[4-[4-chloro-1-methyl-5-trifluoromethyl)-1H-pyrazol-3-yl]-5-fluoro-2-nitrophenoxy]propanoate.

2,4-Difluoro-5-[4-chloro-1-methyl-5-(trifluoromethyl)1H-pyrazol-3-yl]-nitrobenzene(5.0 g, 14.63 mmol) and methyl (R)-(+)-lactate (1.71 g, 16.10 mmol) weredissolved in anhydrous tetrahydrofuran (73 ml) and stirred under icecooling. Sodium hydride (406.7 mg, 95%, 16.10 mmol) was added inportions and solution stirred at ambient temperature for 2 hr. Solutionwas then added to ice water and product separated by filtration (6.1 g,14.33 mmol).

EXAMPLE 8 Preparation of7-Fluoro-6-[4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-2-R-methyl-2H-1,4-benzoxazine-3(4H)-one.

Methyl-2-R-[4-[4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-5-fluoro-2-nitrophenoxy]propanoate(6.0 g, 14.09 mmol) was dissolved in glacial acetic acid (140 ml) andreduced iron powder (3.94 g, 70.45 mmol) was added. Solution was stirredat 80° C. under an atmosphere of nitrogen for 2 hr. Water was added andthe product extracted with ethyl acetate, washed with water and dried(anhydrous sodium sulfate). Evaporation of solvent afforded the titlecompound (5.0 g, 13.74 mmol).

EXAMPLE 9 Preparation of7-Fluoro-6-[4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-2-R-methyl-5-nitro-2H-1,4-benzoxazine-3(4H)-one.

7-Fluoro-6-[4chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-2-R-methyl-2H-1,4-benzoxazine-3(4H)-one(2.5 g, 6.87 mmol) was dissolved in glacial acetic acid (52 ml) andfuming nitric acid (20.8 ml) was slowly added with stirring. Solutionwas stirred at ambient temperature for 2 hr. Ice water was added and theproduct separated by filtration (2.29 g, 5.60 mmol).

EXAMPLE 10 Preparation of5-Amino-7-fluoro-6-[4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-2-R-methyl-2H-1,4-benzoxazine-3(4H)-one.

7-Fluoro-6-[4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-2-R-methyl-5-nitro-2H-1,4-benzoxazine-3(4H)-one(2.29 g, 5.6 mmol) was dissolved in glacial acetic acid (56 ml) andreduced iron powder (1.56 g, 28.0 mmol) was added in portions. Solutionwas stirred at ambient temperature for 16 hr and water was added.Product was extracted with ethyl acetate and washed with water andbrine. Evaporation of solvent furnished a residue, which was trituratedwith ether to afford the title compound (1.79 g. 4.73 mmol).

EXAMPLE 11 Preparation of5-(2-Chloroacetylamino)-6-[4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-7-fluoro-2-R-methyl-2H-1,4-benzoxazine-3(4H)-one.

5-Amino-7-fluoro-6-[4-chloro-1-methyl-5(trifuoromethyl)-1H-pyrazol-3-yl]-2-R-methyl-2H-1,4-benzoxazine-3(4H)-one(1.0 g. 2.64 mmol) was dissolved in anhydrous dioxane (40 ml) andchloroacetyl chloride (0.34 g, 3.01 mmol) was added. Solution wasrefluxed for 2 hr and solvent was then evaporated. The residue wastriturated with ether to afford the title compound (0.90 g, 1.98 mmol).

EXAMPLE 12 Preparation of8-[4-Chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-9-fluoro-2-R-methyl-5H-pyrazino[1,2,3-de]-1,4-benzoxazine-3,6(2H,7H)-dione (Compound No. 1-48).

5-(2-Chloroacetylamino)-6-[4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-7-fluoro-2-R-methyl-2H-1,4-benzoxazine-3(4H)-one(0.90 g, 1.98 mmol) was dissolved in anhydrous dimethylformamide (20 ml)and stirred under ice cooling. Sodium hydride (52.3 mg, 2.18 mmol) wasadded in portions. Solution was stirred at ambient temperature for 2 hrand added to ice water. Product was separated by filtration (0.66 g,1.58 mmol). ¹H NMR data for the compound are listed in Table 4.

The corresponding enantiomeric compound8-[4-Chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-9-fluoro-2-S-methyl-5H-pyrazino[1,2,3-de]-1,4-benzoxazine-3,6(2H,7H)-dione (Compound No. 1-49) was prepared in an identical fashionstarting from methyl (S)-(−)-lactate. The product was determined to bechirally enriched by the NMR analysis using chiral Lanthanide ShiftReagent (LSR). Chirality is retained in the products (Compound Nos. 1-48and 1-49). This was confirmed by NMR analysis of the two compounds withchiral LSR europiumtris[3-(heptafluoropropylhydroxymethylene)-(+)-camphorate] [Eu(HFC)₃].In the presence of LSR (molar ratio 1:1) in deuterated chloroform (0.015mmol solution), the two methyls in compound no. 1-48 (N—CH₃, 4.02 ppm;CH—CH₃, 3.53 ppm) and compound no. 1-49 (N—CH₃, 4.06 ppm; CH—CH₃, 3.40ppm) appear as single set of signals. These resonances in the equimolarmixture of compound no. 1-48 and compound no. 1-49, in the presence ofthe LSR, are resolved as distinct pairs.

EXAMPLE 13 Preparation of5-(2-Bromoisobutyrylamino)-6-[4chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-7-fluoro-2H-1,4benzoxazine-3(4H)-one.

5-Amino-7-fluoro-6-[4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-2H-1,4-benzoxazine-3(4H)-one(1.0 g, 2.64 mmol) was dissolved in anhydrous dioxane (40 ml) and2-bromoisobutyryl bromide (0.67 g, 2.91 mmol) was added. Solution wasrefluxed for 2 hr and solvent was then evaporated. The residue wastriturated with ether to afford the title compound (1.02 g, 1.99 mmol).

EXAMPLE 14 Preparation of8-[4-Chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-5,5-dimethyl-9-fluoro-5H-pyrazino[1,2,3-de]-1,4-benzoxazine-3,6(2H,7H)-dione (Compound No. 1-15).

5-(2-Bromoisobutyrylamino)-6-[4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-7-fluoro-2H-1,4-benzoxazine-3(4H)-one(1.15 g, 2.24 mmol) was dissolved in anhydrous acetonitrile (50 ml) andpotassium iodide (0.45 g, 2.70 mmol) and potassium carbonate (0.37 g,2.70 mmol) were added. Solution was refluxed for 2 hr and water wasadded. Product was extracted with ethyl acetate and solvent evaporated.Column chromatography on silica gel using hexane-ethyl acetate (7:3) aseluent afforded the title compound (84.0 mg, 0.19 mmol).

Using the procedures as described in processes A-D and Examples 1-4, thecompounds of this invention can be readily prepared. Tables 1-3 liststructures for few representative examples of this invention.

TABLE 1

No. Y R R₆ R₇ R₁₂ R₁₃ Q R₁ R₂ R₃ R₄ R₅ 1-1 F H H H H H Q1 CH₃ CF₃ H O O1-2 F H H H H CH₃ Q1 CH₃ CF₃ H O O 1-3 F H H H CH₃ CH₃ Q1 CH₃ CF₃ H O O1-4 F H H H H CH₂CH₃ Q1 CH₃ CF₃ H O O 1-5 F H H H CH₂CH₃ CH₂CH₃ Q1 CH₃CF₃ H O O 1-6 F H H H H CH₂Cl Q1 CH₃ CF₃ H O O 1-7 F H H H H CH₂OCH₃ Q1CH₃ CF₃ H O O 1-8 F H H H H CH═CH₂ Q1 CH₃ CF₃ H O O 1-9 F H H H H phenylQ1 CH₃ CF₃ H O O 1-10 F H H H phenyl phenyl Q1 CH₃ CF₃ H O O 1-11 F CH₃H H H H Q1 CH₃ CF₃ H O O 1-12 F H H H H H Q1 NH₂ CF₃ H O O 1-13 F H H HH H Q3 CH₃ CF₃ Cl — — 1-14 F H H H H CH₃ Q3 CH₃ CF₃ Cl — — 1-15 F H H HCH₃ CH₃ Q3 CH₃ CF₃ Cl — — 1-16 F H H H H CH₂CH₃ Q3 CH₃ CF₃ Cl — — 1-17 FH H H CH₂CH₃ CH₂CH₃ Q3 CH₃ CF₃ Cl — — 1-18 F H H H H CH₂Cl Q3 CH₃ CF₃ Cl— — 1-19 F H H H H CH₂OCH₃ Q3 CH₃ CF₃ Cl — — 1-20 F H H H H CH═CH₂ Q3CH₃ CF₃ Cl — — 1-21 F H H H H phenyl Q3 CH₃ CF₃ Cl — — 1-22 F H H Hphenyl phenyl Q3 CH₃ CF₃ Cl — — 1-23 F CH₃ H H H H Q3 CH₃ CF₃ Cl — —1-24 F H H H H H Q3 CH₃ CF₃ Br 1-25 F H H H H H Q3 CH₃ OCHF₂ Cl — — 1-26F H H H H CH₃ Q3 CH₃ OCHF₂ Cl — — 1-27 F H H H CH₃ CH₃ Q3 CH₃ OCHF₂ Cl —— 1-28 F H H H H CH₂CH₃ Q3 CH₃ OCHF₂ Cl — — 1-29 F H H H CH₂CH₃ CH₂CH₃Q3 CH₃ OCHF₂ Cl — — 1-30 F H H H H CH₂Cl Q3 CH₃ OCHF₂ Cl — — 1-31 F H HH H CH₂OCH₃ Q3 CH₃ OCHF₂ Cl — — 1-32 F H H H H CH═CH₂ Q3 CH₃ OCHF₂ Cl —— 1-33 F H H H H phenyl Q3 CH₃ OCHF₂ Cl — — 1-34 F H H H phenyl phenylQ3 CH₃ OCHF₂ Cl — — 1-35 F CH₃ H H H H Q3 CH₃ OCHF₂ Cl — — 1-36 F H H HH H Q3 CH₃ OCHF₂ Br 1-37 F H H H H H Q2 — — — — — 1-38 F H H H H CH₃ Q2— — — — — 1-39 F H H H CH₃ CH₃ Q2 — — — — — 1-40 F H H H H CH₂CH₃ Q2 — —— — — 1-41 F H H H CH₂CH₃ CH₂CH₃ Q2 — — — — — 1-42 F H H H H CH₂Cl Q2 —— — — — 1-43 F H H H H CH₂OCH₃ Q2 — — — — — 1-44 F H H H H CH═CH₂ Q2 — —— — — 1-45 F H H H H phenyl Q2 — — — — — 1-46 F H H H phenyl phenyl Q2 —— — — — 1-47 F CH₃ H H H H Q2 — — — — — 1-48 F H H R-CH₃ H H Q3 CH₃ CF₃Cl — — 1-49 F H H S-CH₃ H H Q3 CH₃ CF₃ Cl — — 1-50 F H H R-CH₃ H CH₃ Q3CH₃ CF₃ Cl — — 1-51 F H H S-CH₃ H CH₃ Q3 CH₃ CF₃ Cl — — 1-52 F H CH₃ CH₃H H Q3 CH₃ CF₃ Cl — — 1-53 F H H R-CH₃ H CH(CH₃)₂ Q3 CH₃ CF₃ Cl — — 1-54F H CH₃ CH₃ H CH₃ Q3 CH₃ CF₃ Cl — — 1-55 F H H R-CH₃ H H Q3 CH₃ OCHF₂ Cl— — 1-56 F H H S-CH₃ H H Q3 CH₃ OCHF₂ Cl — — 1-57 F H H R-CH₃ H CH₃ Q3CH₃ OCHF₂ Cl — — 1-58 F H H S-CH₃ H CH₃ Q3 CH₃ OCHF₂ Cl — — 1-59 F H CH₃CH₃ H H Q3 CH₃ OCHF₂ Cl — — 1-60 F H CH₃ CH₃ H CH₃ Q3 CH₃ OCHF₂ Cl — —1-61 F H CH₃ CH₃ H CH₂CH₃ Q3 CH₃ OCHF₂ Cl — — 1-62 F CH₃ H H H CH₃ Q3CH₃ OCHF₂ Cl — — 1-63 F H H H H H Q9 H CF₃ Cl — — 1-64 F H H H H CH₃ Q9H CF₃ Cl — — 1-65 F H H H CH₃ CH₃ Q9 H CF₃ Cl — — 1-66 F H H H H CH₂CH₃Q9 H CF₃ Cl — — 1-67 F H H H CH₂CH₃ CH₂CH₃ Q9 H CF₃ Cl — — 1-68 F H H HH phenyl Q9 H CF₃ Cl — — 1-69 F H H CH₃ H H Q9 H CF₃ Cl — — 1-70 F H HCH₃ H CH₃ Q9 H CF₃ Cl — — 1-71 F H CH₃ CH₃ H H Q9 H CF₃ Cl — — 1-72 F HCH₃ CH₃ H CH₃ Q9 H CF₃ Cl — — 1-73 F H H H H H Q5 CHF₂ CH₃ — — — 1-74 FH H H H CH₃ Q5 CHF₂ CH₃ — — — 1-75 F H H H H CH₂CH₃ Q5 CHF₂ CH₃ — — —1-76 F H H H H H Q4 (CH₂)₃F — — — — 1-77 F H H H H CH(CH₃)₂ Q1 CH₃ CF₃ HO O 1-78 F H H H H CH(CH₃)₂ Q2 — — — — — 1-79 F H H H H Cl Q3 CH₃ OCHF₂Cl — —

TABLE 2

No. Y R R₄ R₇ R₁₂ R₁₃ Q R₁ R₂ R₃ R₄ R₅ 2-1 F H H H H H Q1 CH₃ CF₃ H O O2-2 F H H H H CH₃ Q1 CH₃ CF₃ H O O 2-3 F H H H CH₃ CH₃ Q1 CH₃ CF₃ H O O2-4 F H H H H CH₂CH₃ Q1 CH₃ CF₃ H O O 2-5 F H H H CH₂CH₃ CH₂CH₃ Q1 CH₃CF₃ H O O 2-6 F H H H H CH₂Cl Q1 CH₃ CF₃ H O O 2-7 F H H H H CH₂OCH₃ Q1CH₃ CF₃ H O O 2-8 F H H H H CH═CH₂ Q1 CH₃ CF₃ H O O 2-9 F H H H H phenylQ1 CH₃ CF₃ H O O 2-10 F H H H phenyl phenyl Q1 CH₃ CF₃ H O O 2-11 F CH₃H H H H Q1 CH₃ CF₃ H O O 2-12 F H H H H H Q1 NH₂ CF₃ H O O 2-13 F H H HH H Q3 CH₃ CF₃ Cl — — 2-14 F H H H H CH₃ Q3 CH₃ CF₃ Cl — — 2-15 F H H HCH₃ CH₃ Q3 CH₃ CF₃ Cl — — 2-16 F H H H H CH₂CH₃ Q3 CH₃ CF₃ Cl — — 2-17 FH H H CH₂CH₃ CH₂CH₃ Q3 CH₃ CF₃ Cl — — 2-18 F H H H H CH₂Cl Q3 CH₃ CF₃ Cl— — 2-19 F H H H H CH₂OCH₃ Q3 CH₃ CF₃ Cl — — 2-20 F H H H H CH═CH₂ Q3CH₃ CF₃ Cl — — 2-21 F H H H H phenyl Q3 CH₃ CF₃ Cl — — 2-22 F H H Hphenyl phenyl Q3 CH₃ CF₃ Cl — — 2-23 F CH₃ H H H H Q3 CH₃ CF₃ Cl — —2-24 F H H H H H Q3 CH₃ CF₃ Br 2-25 F H H H H H Q3 CH₃ OCHF₂ Cl — — 2-26F H H H H CH₃ Q3 CH₃ OCHF₂ Cl — — 2-27 F H H H CH₃ CH₃ Q3 CH₃ OCHF₂ Cl —— 2-28 F H H H H CH₂CH₃ Q3 CH₃ OCHF₂ Cl — — 2-29 F H H H CH₂CH₃ CH₂CH₃Q3 CH₃ OCHF₂ Cl — — 2-30 F H H H H CH₂Cl Q3 CH₃ OCHF₂ Cl — — 2-31 F H HH H CH₂OCH₃ Q3 CH₃ OCHF₂ Cl — — 2-32 F H H H H CH═CH₂ Q3 CH₃ OCHF₂ Cl —— 2-33 F H H H H phenyl Q3 CH₃ OCHF₂ Cl — — 2-34 F H H H phenyl phenylQ3 CH₃ OCHF₂ Cl — — 2-35 F CH₃ H H H H Q3 CH₃ OCHF₂ Cl — — 2-36 F H H HH H Q3 CH₃ OCHF₂ Br 2-37 F H H H H H Q2 — — — — — 2-38 F H H H H CH₃ Q2— — — — — 2-39 F H H H CH₃ CH₃ Q2 — — — — — 2-40 F H H H H CH₂CH₃ Q2 — —— — — 2-41 F H H H CH₂CH₃ CH₂CH₃ Q2 — — — — — 2-42 F H H H H CH₂Cl Q2 —— — — — 2-43 F H H H H CH₂OCH₃ Q2 — — — — — 2-44 F H H H H CH═CH₂ Q2 — —— — — 2-45 F H H H H phenyl Q2 — — — — — 2-46 F H H H phenyl phenyl Q2 —— — — — 2-47 F CH₃ H H H H Q2 — — — — —

TABLE 3

No. Y R R₆ R₁₂ R₁₃ Q R₁ R₂ R₃ R₄ R₅ 3-1 F H H H H Q1 CH₃ CF₃ H O O 3-2 FH H H CH₃ Q1 CH₃ CF₃ H O O 3-3 F H H CH₃ CH₃ Q1 CH₃ CF₃ H O O 3-4 F H HH CH₂CH₃ Q1 CH₃ CF₃ H O O 3-5 F H H CH₂CH₃ CH₂CH₃ Q1 CH₃ CF₃ H O O 3-6 FH H H CH₂Cl Q1 CH₃ CF₃ H O O 3-7 F H H H CH₂OCH₃ Q1 CH₃ CF₃ H O O 3-8 FH H H CH═CH₂ Q1 CH₃ CF₃ H O O 3-9 F H H H phenyl Q1 CH₃ CF₃ H O O 3-10 FH H phenyl phenyl Q1 CH₃ CF₃ H O O 3-11 F CH₃ H H H Q1 CH₃ CF₃ H O O3-12 F H H H H Q1 NH₂ CF₃ H O O 3-13 F H H H H Q3 CH₃ CF₃ Cl — — 3-14 FH H H CH₃ Q3 CH₃ CF₃ Cl — — 3-15 F H H CH₃ CH₃ Q3 CH₃ CF₃ Cl — — 3-16 FH H H CH₂CH₃ Q3 CH₃ CF₃ Cl — — 3-17 F H H CH₂CH₃ CH₂CH₃ Q3 CH₃ CF₃ Cl —— 3-18 F H H H CH₂Cl Q3 CH₃ CF₃ Cl — — 3-19 F H H H CH₂OCH₃ Q3 CH₃ CF₃Cl — — 3-20 F H H H CH═CH₂ Q3 CH₃ CF₃ Cl — — 3-21 F H H H phenyl Q3 CH₃CF₃ Cl — — 3-22 F H H phenyl phenyl Q3 CH₃ CF₃ Cl — — 3-23 F CH₃ H H HQ3 CH₃ CF₃ Cl — — 3-24 F H H H H Q3 CH₃ CF₃ Br 3-25 F H H H H Q3 CH₃OCHF₂ Cl — — 3-26 F H H H CH₃ Q3 CH₃ OCHF₂ Cl — — 3-27 F H H CH₃ CH₃ Q3CH₃ OCHF₂ Cl — — 3-28 F H H H CH₂CH₃ Q3 CH₃ OCHF₂ Cl — — 3-29 F H HCH₂CH₃ CH₂CH₃ Q3 CH₃ OCHF₂ Cl — — 3-30 F H H H CH₂Cl Q3 CH₃ OCHF₂ Cl — —3-31 F H H H CH₂OCH₃ Q3 CH₃ OCHF₂ Cl — — 3-32 F H H H CH═CH₂ Q3 CH₃OCHF₂ Cl — — 3-33 F H H H phenyl Q3 CH₃ OCHF₂ Cl — — 3-34 F H H phenylphenyl Q3 CH₃ OCHF₂ Cl — — 3-35 F CH₃ H H H Q3 CH₃ OCHF₂ Cl — — 3-36 F HH H H Q3 CH₃ OCHF₂ Br 3-37 F H H H H Q2 — — — — — 3-38 F H H H CH₃ Q2 —— — — — 3-39 F H H CH₃ CH₃ Q2 — — — — — 3-40 F H H H CH₂CH₃ Q2 — — — — —3-41 F H H CH₂CH₃ CH₂CH₃ Q2 — — — — — 3-42 F H H H CH₂Cl Q2 — — — — —3-43 F H H H CH₂OCH₃ Q2 — — — — — 3-44 F H H H CH═CH₂ Q2 — — — — — 3-45F H H H phenyl Q2 — — — — — 3-46 F H H phenyl phenyl Q2 — — — — — 3-47 FCH₃ H H H Q2 — — — — —

Table 4 lists some of the characterization data for a few representativecompounds of this invention.

TABLE 4 ¹H NMR data No. NMR (CDCl₃, 300 MHz) ppm 1-1  3.55(3H, s),4.30(1H, d, J=18.4Hz), 4.41(1H, d, J=18.4Hz), 4.71(2H, s), 6.36(1H, s),6.65 (1H, d, J=9.6Hz), 10.31(1H, s) 1-2  1.30(3H, m), 3.44(3H, s),4.77(2H, m), 4.91(1H, m), 6.60, 6.63(1H, each s), 6.91, 6.93 (1H, eachd, J=10.2Hz), 10.98, 11.01(1H, each s) 1-4  (CD₃)₂SO 0.81(3H, m),1.72(2H, m), 3.43(3H, s), 4.70-4.90(3H, m), 6.60, 6.62(1H, each s),6.91, 6.93(1H, each d, J=10.2Hz), 11.01, 11.05(1H, each s) 1-13 4.11(3H,s), 4.55(2H, s), 4.73(2H, s), 6.61(1H, d, J=9.9Hz), 8.45(1H, s) 1-151.94(6H, s), 4.10(3H, s), 4.61(2H, s), 6.55(1H, d, J=9.8Hz), 8.27(1H, s)1-21 4.08(3H, s), 4.65(1H, d, J=15.0Hz), 4.83(1H, d, J=15.0Hz), 6.25(1H,s), 6.67(1H, d, J=9.9Hz), 7.32(br s, 5H), 8.58(1H, s) 1-25 3.88(3H, s),4.54(2H, s), 4.72(2H, s), 6.59(1H, d, J=10.1Hz), 6.74(1H, t, J=72.1Hz),8.90 (1H, s) 1-26 1.48(3H, d, J=7.0Hz), 3.88(3H, s), 4.56(1H, d,J=14.8Hz), 4.78(1H, d, J=14.8Hz), 5.25 (1H, m), 6.60(1H, d, J=10.0 Hz),6.75(1H, t, J=72.1Hz), 8.90(1H, s) 1-27 1.94(6H, s), 3.87(3H, s),4.60(2H, s), 6.53(1H, d, J=9.9Hz), 6.75(1H, t, J=72.1Hz), 8.76 (1H, s)1-28 0.97(3H, t, J=7.5Hz), 1.88(2H, m), 3.88(3H, s), 4.55(1H, d,J=14.9Hz), 4.81(1H, d, J=14.9Hz), 5.17(1H, t, J=6.6Hz), 6.61(1H, d,J=10.1Hz), 6.75(1H, t, J=72.1Hz), 8.92 (1H, s) 1-33 3.85(3H, s),4.64(1H, d, J=15.0Hz), 4.82(1H, d, J=15.0Hz), 6.24(1H, s), 6.65(1H, d,J=10.1Hz), 6.73(1H, t, J=72.1Hz), 7.32(5H, br s), 9.09(1H, s) 1-37(CD₃)₂SO 1.75(4H, m), 2.34(4H, m), 4.40(2H, s), 4.78(2H, s), 6.86(1H, d,J=10.2Hz), 10.99(1H, s) 1-38 CDCl₃+CD₃OD 1.48(3H, d, J=6.9Hz), 1.87(4H,m), 2.45(4H, m), 4.60(1H, d, J=14.8Hz), 4.77(1H, d, J=14.8Hz), 5.13(1H,m), 6.64(1H, d, J=9.7Hz), 7.49(1H, s) 1-48 1.64(3H, d, J=6.8Hz),4.11(3H, s), 4.40(1H, d, J=18.2Hz), 4.63(1H, d, J=18.2Hz), 4.77 (1H, q,J=6.7Hz), 6.61(1H, d, J=9.9Hz), 8.43(1H, s) 1-50 1.46(m) and 1.71(d,J=6.6Hz) (6H combined), 4.11(3H, s), 4.57(q) and 4.94(q) (1H combined),5.21(1H, m), 6.62(1H, pair of d), 8.42(1H, s) 1-52 (CD₃)₂SO 1.48(6H, s),4.03(3H, s), 4.37(2H, s), 6.79(1H, d, J=10.0Hz), 10.13(1H, s) 1-531.03(6H, m), 1.50 and 1.78(3H combined, m), 2.13(1H, m), 4.16(3H, s),4.59 and 5.04(2H, each m), 6.68(1H, d, J=9.8Hz), 8.47(1H, br s) 1-54(CD₃)₂SO 1.30(3H, d, J=7.0Hz), 1.35(3H, s), 1.61(3H, s), 4.04(3H, s),4.85(1H, q, J=7.0 Hz), 6.84(1H, d, J=10.1Hz), 10.24(1H, s) 1-55 (CD₃)₂SO1.49(3H, d, J=6.4Hz), 3.77(3H, s), 4.29(1H, d, J=17.5Hz), 4.47(1H, d,J=17.5 Hz), 4.89(1H, m), 6.82(1H, d, J=9.8Hz), 7.29(1H, t, J=71.1Hz),9.93(1H, s) 1-57 (CD₃)₂SO 1.20-1.60(6H, m), 3.78(3H, s), 4.80-5.10(2H,m), 6.85(1H, m), 7.30(1H, t, J=71.2Hz), 10.05(1H, m) 1-59 (CD₃)₂SO1.48(6H, s), 3.77(3H, s), 4.36(2H, s), 6.77(1H, d, J=10.1Hz), 7.30(1H,t, J=71.2 Hz), 9.91(1H, s) 1-60 (CD₃)₂SO 1.30(3H, d, J=7.0Hz), 1.34(3H,s), 1.60(3H, s), 3.78(3H, s), 4.86(1H, m), 6.81 (1H, d, J=10.1Hz),7.29(1H, t, J=71.3Hz), 10.03(1H, s) 1-61 (CD₃)₂SO 0.82(3H, t, J=7.5Hz),1.34(3H, s), 1.62(3H, s), 1.63-1.80(2H, m), 3.78(3H, s), 4.81(1H, m),6.81(1H, d, J=10.1Hz), 7.29(1H, t, J=71.2Hz), 10.09(1H, s) 1-62 1.39(3H,d, J=7.0Hz), 2.83(3H, br s), 3.86(3H, s), 4.56(1H, d, J=14.4Hz),4.77(1H, d, J=14.4Hz), 5.35(1H, m), 6.69(1H, d, J=9.5Hz), 6.73(1H, t,J=72.0Hz) 1-63 (CD₃)₂SO 4.36(1H, d, J=17.6Hz), 4.46(1H, d, J=17.6Hz),4.80(1H, s), 6.86(1H, d, J=10.2 Hz), 8.63(1H, m), 9.05(1H, m), 10.33(1H,s) 1-64 (CD₃)₂SO 1.32(3H, m), 4.78(2H, m), 4.93(1H, m), 6.91(1H, d,J=10.2Hz), 8.64(1H, m), 9.07(1H, m), 10.45(1H, m) 1-66 (CD₃)₂SO 0.86(3H,m), 1.73(2H, m), 4.70-4.90(3H, m), 6.91(1H, d, J=10.2Hz), 8.64(1H, m),9.08(1H, m), 10.49(1H, m) 1-68 (CD₃)₂SO 4.85(2H, m), 5.97(1H, m),6.97(1H, m), 7.20-7.50(5H, m), 8.63(1H, m), 9.05 (1H, m), 10.67(1H, m)1-73 (CD₃)₂SO 2.37(3H, s), 4.33(1H, d=17.0Hz), 4.47(1H, d, J=17.0Hz),4.79(2H, s), 6.89(1H, d, J=10.3Hz), 7.50(1H, t, J=56.9Hz), 10.93(1H, s)1-74 (CD₃)₂SO 1.33(3H, d, J=6.9Hz), 2.38(3H, s), 4.72(1H, d, J=14.7Hz),4.82(1H, d, J=14.7 Hz), 4.93(1H, m), 6.94(1H, d, J=10.3Hz), 7.51(1H, t,J=56.9Hz), 11.01(1H, s) 1-75 (CD₃)₂SO 0.83(3H, t, J=7.4Hz), 1.75(2H, m),2.38(3H, s), 4.60-4.90(3H, m), 6.95(1H, d, J=10.3Hz), 7.51(1H, t,J=56.9Hz), 11.06(1H, s) 1-76 (CD₃)₂SO 2.24(1H, m), 2.32(1H, m), 4.10(2H,m), 4.46(2H, s), 4.54(1H, m), 4.70(1H, m), 4.77(2H, s), 6.71(1H, d,J=9.9Hz), 11.10(1H, s) 1-77 0.85-1.00(6H, m), 2.07(1H, m), 3.57(3H, m),4.51(1H, m), 4.70-4.90(2H, m), 6.36(1H, m), 6.68(1H, d, J=9.6Hz),10.49(1H, m) 1-78 0.80-1.10(6H, m), 1.88(4H, m), 2.00-2.20(1H, m),2.44(4H, m), 4.40-4.90(3H, m), 6.63 (1H, d, J=9.7Hz), 9.51(1H, m)

Herbicidal Activity

The compounds of the present invention exhibit excellent herbicidaleffects when used as an active ingredient of a herbicide. The herbicidecan be used for a wide range of applications, for example on crop landssuch as paddy fields, upland farms, orchards and mulberry fields, andnon-crop lands such as forests, farm roads, playgrounds, and factorysites. The application method may be suitably selected for soiltreatment application and foliar application.

The compounds of the present invention are capable of controllingnoxious weeds including grass (gramineae) such as barnyardgrass(Echinochloa crus-gall), large crabgrass (Digitaria sanguinalis), greenfoxtail (Setaria viridis), goosegrass (Eleusine indica L.), wild oat(Avena fatua L.), Johnsongrass (Sorghum halepense), quackgrass(Agropyron repens), alexandergrass (Brachiaria plantaginea), paragrass(Panicum purpurascen), sprangletop (Leptochloa chinensis) and redsprangletop (Leptochloa panicea); sedges (or Cyperaceae) such as riceflatsedge (Cyperus iria L.), purple nutsedge (Cyperus rotundus L.),Japanese bulrush (Scirpus Juncoides), flatsedge (Cyperus serotinus),small-flower umbrellaplant (Cyperus difformis), slender spikerush(Eleocharis acicularis), and water chestnut (Eleocharis kuroguwai);alismataceae such as Japanese ribbon wapato (Sagittaria pygmaea),arrow-head (Sagittaria trifolia) and narrowleaf waterplantain (Alismacanaliculatum); pontederiaceae such as monochoria (Monochoria vaginalis)and monochoria species (Monochoria korsakowii); scrophulariaceae such asfalse pimpernel (Lindernia pyxidaria) and abunome (Dopatrium Junceum);lythraceae such as toothcup (Rotala indica) and red stem (Ammanniamultiflora); and broadleaves such as redroot pigweed (Amaranthusretroflexus), velvetleaf (Abutilon theophrasti), morningglory (Ipomoeahederacea), lambsquarters (Chenopodium album), prickly sida (Sidaspinosa L.), common purslane (Portulaca oleracea L.), slender amaranth(Amaranthus viridis L.), sicklepod (Cassia obtusifolia), blacknightshade (Solanum nigrum L.), pale smartweed (Polygonum LapathifoliumL.), common chickweed (Stellaria media L.), common cocklebur (Xanthiumstrumarium L.), flexuous bittercress (Cardamine flexuosa WITH.), henbit(Lamium amplexicaule L.) and threeseeded copperleaf (Acalypha australisL.). Accordingly, it is useful for controlling noxious weedsnon-selectively or selectively in the cultivation of a crop plant suchas corn (Zea mays L.), soybean (Glycine max Merr.), cotton (Gossypiumspp.), wheat (Triticum spp.), rice (Oryza sativa L.), barley (Hordeumvulgare L.), oat (Avena sativa L.), sorgo (Sorghum bicolor Moench), rape(Brassica napus L.), sunflower (Helianthus annuus L.), sugar beet (Betavulgaris L.), sugar cane (Saccharum officinarum L.), Japanese lawngrass(Zoysia Japonica stend), peanut (Arachis hypogaea L.) or flax (Linumusitatissimum L.).

For use as herbicides, the active ingredients of this invention areformulated into herbicidal compositions by mixing herbicidally activeamounts with inert ingredients known to the art to facilitate either thesuspension, dissolution or emulsification of the active ingredient forthe desired use. The type of formulation prepared recognizes the factsthat formulation, crop and use pattern all can influence the activityand utility of the active ingredient in a particular use. Thus foragricultural use the present herbicidal compounds may be formulated aswater dispersible granules, granules for direct application to soils,water soluble concentrates, wettable powders, dusts, solutions,emulsifiable concentrates (EC), microemulsion, suspoemulsion, invertemulsion or other types of formulations depending on the desired weedtargets, crops and application methods.

These herbicidal formulations may be applied to the target area (wheresuppression of unwanted vegetation is the objective) as dusts, granulesor water or solvent diluted sprays. These formulation may contain aslittle as 0.1% to as much as 97% active ingredient by weight.

Dusts are admixtures of the active ingredient with finely groundmaterials such as clays (some examples include kaolin andmontmorillonite clays), talc, granite dust or other organic or inorganicsolids which act as dispersants and carriers for the active ingredient;these finely ground materials have an average particle size of less than50 microns. A typical dust formulation will contain 1% active ingredientand 99% carrier.

Wettable powders are composed of finely ground particles which disperserapidly in water or other spray carriers. Typical carriers includekaolin clays, Fullers earth, silicas and other absorbent, wettableinorganic materials. Wettable powders can be prepared to contain from 1to 90% active ingredient, depending on the desired use pattern and theabsorbability of the carrier. Wettable powders typically contain wettingor dispersing agents to assist dispersion in water or other carriers.

Water dispersible granules are granulated solids that freely dispersewhen mixed in water. This formulation typically consists of the activeingredient (0.1% to 95% active ingredient), a wetting agent (1-15% byweight), a dispersing agent (1 to 15% by weight) and an inert carrier(1-95% by weight). Water dispersible granules can be formed by mixingthe ingredients intimately then adding a small amount of water on arotating disc (said mechanism is commercially available) and collectingthe agglomerated granules. Alternatively, the mixture of ingredients maybe mixed with an optimal amount of liquid (water or other liquid) andpassed through an extruder (said mechanism is commercially available)equipped with passages which allow for the formation of small extrudedgranules. Alternatively, the mixture of ingredients can be granulatedusing a high speed mixer (said mechanism is commercially available) byadding a small amount of liquid and mixing at high speeds to affectagglomeration. Alternatively, the mixture of ingredients can bedispersed in water and dried by spraying the dispersion through a heatednozzle in a process known as spray drying (spray drying equipment iscommercially available). After granulation the moisture content ofgranules is adjusted to an optimal level (generally less than 5%) andthe product is sized to the desired mesh size.

Granules are granulated solids that do not disperse readily in water,but instead maintain their physical structure when applied to the soilusing a dry granule applicator. These granulated solids may be made ofclay, vegetable material such as corn cob grits, agglomerated silicas orother agglomerated organic or inorganic materials or compounds such ascalcium sulfate. The formulation typically consists of the activeingredient (1 to 20%) dispersed on or absorbed into the granule. Thegranule may be produced by intimately mixing the active ingredient withthe granules with or without a sticking agent to facilitate adhesion ofthe active ingredient to the granule surface, or by dissolving theactive ingredient in a solvent, spraying the dissolved active ingredientand solvent onto the granule then drying to remove the solvent. Granularformulations are useful where in-furrow or banded application isdesired.

Emulsifiable concentrates (EC) are homogeneous liquids composed of asolvent or mixture of solvents such as xylenes, heavy aromatic naphthas,isophorone or other proprietary commercial compositions derived frompetroleum distillates, the active ingredient and an emulsifying agent oragents. For herbicidal use, the EC is added to water (or other spraycarrier) and applied as a spray to the target area. The composition ofan EC formulation can contain 0.1% to 95% active ingredient, 5 to 95%solvent or solvent mixture and 1 to 20% emulsifying agent or mixture ofemulsifying agents.

Suspension concentrate (also known as flowable) formulations are liquidformulations consisting of a finely ground suspension of the activeingredient in a carrier, typically water or a non-aqueous carrier suchas an oil. Suspension concentrates typically contain the activeingredient (5 to 50% by weight), carrier, wetting agent, dispersingagent, anti-freeze, viscosity modifiers and pH modifiers. Forapplication, suspension concentrates are typically diluted with waterand sprayed on the target area.

Solution concentrates are solutions of the active ingredient (1 to 70%)in solvents which have sufficient solvency to dissolve the desiredamount of active ingredient Because they are simple solutions withoutother inert ingredients such as wetting agents, additional additives areusually added to the spray tank mix before spraying to facilitate properapplication.

Microemulsions are solutions consisting of the active ingredient (1 to30%) dissolved in a surfactant or emulsifier, without any additionalsolvents. There are no additional solvents added to this formulation.Microemulsions are particularly useful when a low odor formulation isrequired such as in residential turfgrass applications.

Suspoemulsions are combinations of two active ingredients. One activeingredient is made as a suspension concentrate (1-50% active ingredient)and the second active is made as a emulsifiable concentrate (0.1 to20%). A reason for making this kind of formulation is the inability tomake an EC formulation of the first ingredient due to poor solubility inorganic solvents. The suspoemulsion formulation allows for thecombination of the two active ingredients to be packaged in onecontainer, thereby minimizing packaging waste and giving greaterconvenience to the product user.

The herbicidal compounds of this invention may be formulated or appliedwith insecticides, fungicides, acaricides, nematicides, fertilizers,plant growth regulators or other agricultural chemicals. Certain tankmix additives, such as spreader stickers, penetration aids, wettingagents, surfactants, emulsifiers, humectants and UV protectants maybeadded in amounts of 0.01% to 5% to enhance the biological activity,stability, wetting, spreading on foliage or uptake of the activeingredients on the target area or to improve the suspensibility,dispersion, redispersion, emulsifiability, UV stability or otherphysical or physico-chemical property of the active ingredient in thespray tank, spray system or target area.

The compositions of the present invention may be used in admixture withor in combination with other agricultural chemicals, fertilizers,adjuvants, surfactants, emulsifiers, oils, polymers orphytotoxicity-reducing agents such as herbicide safeners. In such acase, they may exhibit even better effects or activities. As otheragricultural chemicals, herbicides, fungicides, antibiotics, planthormones, plant growth regulators, insecticides, or acaricides may, forexample, be mentioned. Especially with herbicidal compositions havingthe compounds of the present invention used in admixture with or incombination with one or more active ingredients of other herbicides, itis possible to improve the herbicidal activities, the range ofapplication time(s) and the range of applicable weed types. Further, thecompounds of the present invention and an active ingredient of anotherherbicide may be separately formulated so they may be mixed for use atthe time of application, or both may be formulated together. The presentinvention covers such herbicidal compositions.

The blend ratio of the compounds of the present invention with theactive ingredient of other herbicides can not generally be defined,since it varies depending on the time and method of application, weatherconditions, soil type and type of formulation. However one activeingredient of other herbicide may be incorporated usually in an amountof 0.01 to 100 parts by weight, per one part by weight of the compoundsof the present invention. Further, the total dose of all of the activeingredients is usually from 1 to 10000 g/ha, preferably from 5 to 500g/ha The present invention covers such herbicidal compositions.

As the active ingredients of other herbicides, the following (commonname) may be mentioned. Herbicidal compositions having the compounds ofthe present invention used in combination with other herbicides, mayoccasionally exhibit a synergistic effect.

Those that are believed to exhibit herbicidal effects by disturbingauxin activities of plants, including a phenoxy acetic acid type such as2,4-D, 2,4-DB, 2,4-DP, MCPA, MCPP, MCPB or naproanilide (including thefree acids, esters or salts thereof), an aromatic carboxylic type suchas 2,3,6 TBA, dicamba, dichlobenil, a pyridine type such as picloram(including free acids and salts thereof), triclopyr or clopyralid andothers such as naptalam, benazolin, quinclorac, quinmerac ordiflufenzopyr (BAS 654H).

Those that are believed to exhibit herbicidal effects by inhibitingphotosynthesis of plants including a urea type such as diuron, linuron,isoproturon, chlorotoluron, metobenzuron, tebuthiuron or fluometuron, atriazine type such as simazine, atrazine, cyanazine, terbuthylazine,atraton, hexazinone, metribuzin, simetryn, ametryn, prometryn,dimethametryn or triaziflam, a uracil type such as bromacil, terbacil orlenacil, an anilide type such as propanil or cypromid, a carbamate typesuch as desmedipham or phenmedipham, a hydroxybenzonitrile type such asbromoxynil or ioxynil, and others such as pyridate, bentazon andmethazole.

A quaternary ammonium salt type such as paraquat, diquat or difenzoquat,which is believed to be converted to free radicals by itself to formactive oxygen in the plant and thus to exhibit quick herbicidal effects.

Those which are believed to exhibit herbicidal effects by inhibitingchlorophyll biosynthesis in plants and abnormally accumulating aphotsensitizing substance in the plant body, including a diphenyl ethertype such as nitrofen, lactofen, acifluorfen-sodium, oxyfluorfen,fomesafen, bifenox, or chlomethoxyfen, a cyclic imide type such aschlorphthalim, flumioxazin, cinidon-ethyl, or flumiclorac-pentyl, andothers such as oxadiazon, sulfentrazone, thidiazimin, azafenidin,carfentrazone, isopropazole, fluthiacet-methyl, pentoxazone,pyraflufen-ethyl and oxadiargyl.

Those which are believed to exhibit herbicidal effects characterized bywhitening activities by inhibiting chromogenesis of plants such ascarotenoids including a pyridazinone type such as norflurazon,chloridazon or metflurazon, a pyrazol type such as pyrazolate,pyrazoxyfen or benzofenap, and others such as fluridone, fluramone,diflufencam, methoxyphenone, clomazone, amitrole, sulcotrione,mesotrione, isoxaflutole and isoxachlortole.

Those which exhibit herbicidal effects specifically to gramineous plantsincluding an aryloxyphenoxypropionic acid type (either as a mixture ofisomers or as a resolved isomer) such as diclofop-methyl,pyrofenop-sodium, fluazifop butyl or fluazifop-p-butyl, haloxyfopmethyl,quizalofop-pethyl, quizalafop p-tefuryl, fenoxaprop ethyl orfenoxaprop-p-ethyl, flamprop-M-methyl or flamprop-m-isopropyl orcyhalofop-butyl and a cyclohexanedione type such as alloxydim-sodium,sethoxydim, clethodim, tepraloxydim or tralkoxydim.

Those which are believed to exhibit herbicidal effects by inhibitingamino acid biosynthesis of plants, including a sulfonylurea type such aschlorimuron-ethyl, nicosulfuron, metsulfuron-methyl, triasulfuron,primisulfuron, tribenuron-methyl, chlorosulfuron, bensulfuron-methyl,sulfometuron-methyl, prosulfuron, halosulfuron or halosulfuron-methyl,thifensulfuron-methyl, rimsulfuron, azimsulfuron, flazasulfuron,imazosulfuron, cyclosulfamuron, flupyrsulfuron, iodosulfuron,ethoxysulfuron, flucarbazone, sulfosulfuron, oxasulfuron atriazolopyrimidinesulfonamide type such as flumetsulam, metosulam,chioransulam or chloransulam-methyl, an imidazolinone type such asimazapyr, imazethapyr, imazaquin, imazamox, imazarmeth, imazamethabenzmethyl, a pyrimidinesalicylic acid type such as pyrthiobac-sodium,bispyribac-sodium, pyriminobac-methyl or pyribenzoxim (LGC-40863), andothers such as glyphosate, glyphosate-ammonium,glyphosate-isopropylamine or sulfosate.

Those which are believed to exhibit herbicidal effects by interferingwith the normal metabolism of inorganic nitrogen assimilation such asglufosinate, glufosinate-ammonium, phosphinothricin or bialophos.

Those which are believed to exhibit herbicidal effects by inhibitingcell division of plant cells, including a dinitroaniline type such astrifluralin, oryzalin, nitralin, pendamethalin, ethafluralin, benefinand prodiamine, an amide type such as bensulide, napronamide, andpronamide, a carbarnate type such as propham, chlorpropham, barban, andasulam, an organophosphorous type such as aminoprofos-methyl orbutamifos and others such as DCPA and dithiopyr.

Those which are believed to exhibit herbicidal effects by inhibitingprotein synthesis of plant cells, including a chloroacetanilide typesuch as alachlor, metolachor (including combinations with safeners suchas benoxacor, or resolved isomeric mixtures of metolachlor includingsafeners such as benoxacor) propachlor, acetochlor (includingcombinations with herbicide safeners such as dichlormid or MON 4660 orresolved isomeric mixtures of acetochlor containing safeners such asdichlornid or MON 4660), propisochlor or dimethenarmid or anoxyacetamide type such as flufenacet.

Those in which the mode of action causing the herbicidal effects are notwell understood including the dithiocarbamates such as thiobencarb,EFITC, diallate, triallate, molinate, pebulate, cycloate, butylate,vemrolate or prosulfocarb and miscellaneous herbicides such as MSMA,DSMA, endothall, ethofumesate, sodium chlorate, pelargonic acid andfosamine. A few formulation examples of the present invention are givenas follows:

Ingredient Trade Name Chemical Name Supplier Function % wt./wt.Formulation example 1. Emulsifiable Concentrate Active Ingredient 5.0Toximul H-A Calcium sulfonate and nonionic Stepan Co. Emulsifier 2.5surfactant blend Toximul D-A Calcium sulfonate and nonionic Stepan Co.Emulsifier 7.5 surfactant blend Aromatic 200 Aromatic hydrocarbon ExxonChemical Solvent QS to Co. 100% Formulation example 2. SuspensionConcentrate Active Ingredient 10.0 Proylene glycol Anti-freeze 5.00Antifoam 1530 Silicone defoamer Dow Corning Anti-foam 0.50 Rhodopol 23Xanthan gum Rhone-Poulenc Suspending Aid 0.25 Morwet D-425 Naphthaleneformaldehyde Witco Corp. Dispersant 3.00 condensate Igepal CA-720Octylphenol ethoxylate Rhone-Poulenc Wetting agent 3.00 Proxel GXL 1,2benziso-thiazolin-3-one ICI Americas Preservative 0.25 Water Diluent68.00 Formulation example 3. Wettable Powder Active Ingredient 50.00Geropon T-77 Sodium N-methyl-N-oleoyl Rhone-Poulenc Wetting agent 3.00taurate Lomar PW Naphthalene Sulfonate Henkel Corp. Dispersant 5.00Kaolin clay Kaolin clay J. M. Huber Filler 42.00 Formulation example 4.Water Dispersible Granule Active Ingredient 50.00 Morwet EFW Witco Corp.Wetting agent 2.00 Morwet D-425 Napthalene formaldehyde Witco Corp.Dispersant 10.00 condensate ASP 400 Kaolin Clay Engelhard Corp. Filler38.00

Test Example

A standard greenhouse herbicide activity screening system was used toevaluate the herbicidal efficacy and crop safety of these testcompounds. Seven broadleaf weed species including redroot pigweed(Amaranthus retroflexus, AMR), velvetleaf (Abutilon theophrasti, ABT),sicklepod (Cassia obtusifolia, CAO), ivyleaf morningglory (Ipomoeahederacea, IPH), lambsquarters (Chenopodium album, CHA), common ragweed(Ambrosia artemisiifolia L., AML), and cocklebur (Xanthium strumariunt,XAS) were used as test species. Four grass weed species including greenfoxtail (Setaria viridis, SEV), barnyardgrass (Echinachloa crus-galli,ECC), johnsongrass (Sorghum halepense, SOH), and large crabgrass(Digitaria sanguinalis, DIS) were also used. In addition, four cropspecies, field corn (Zea mays L., var. Dekalb 535, CORN), soybean(Glycine max L., var. Pella 86, SOY), upland rice (Oryza sp.,var.Tebonnet, RICE), and wheat (Triticum aestivum) were included allplants were grown in 10 cm square plastic pots which were filled with asandy loam soil mix.

Pre-emerge Test

For pre-emerge tests, seeds were planted one day prior to application ofthe test compounds. All test compounds were dissolved in acetone andapplied to the test pots in a volume of 187 l/ha. Test materials wereapplied at rates ranging from 8 g ai/ha to 1000 g ai/ha using a tracksprayer equipped with a TJ8001E even flow flat fan spray nozzle. Thisapplication simulates a typical commercial field herbicide application.

Post-emerge Test

For post-emerge tests, seeds were planted 8-21 days prior to the test toallow emergence and good foliage development prior to application of thetest substances. At the time of the post-emerge application, plants ofall species were usually at the 2-3 leaf stage of development. In thepostemerge test, a commercial non-ionic surfactant was also included(0.25% v/v) to enhance wetting of the leaf surfaces of target plants.

At 14 days after application of the test materials, phytotoxicityratings were recorded. A rating scale of 0-100 was used for both pre andpost emerge tests as previously described in Research Methods in WeedScience, 2nd edition, B, Truelove, Ed., Southern Weed Science Society,Auburn University, Auburn, Ala., 1977. Briefly, “0” corresponds to nodamage and “100” corresponds to complete death of all plants in the testunit. This scale was used both to determine efficacy against weedspecies and damage to crop species. Herbicide activity data for variouscompounds of this invention, which are shown by compound No. in Tables1-3, are shown in Tables 5 and 6. The data demonstrate significantdifferences between compounds for both efficacy against weeds andselectivity for crop species. For selected compounds, excellent activityagainst a majority of the weed species was observed with minimal damageto at least one of the crop species.

TABLE 5 Pre-emerge Herbicidal Activity Compd. Rate No. g ai/ha AMR ABTCAO IPH CHA AML XAS SEV ECC SOH DIS CORN SOY RICE WHEAT 1-1  250 100 100100 100 100 100 99 100 100 100 100 100 100 100 100 1-2  250 100 100 99100 100 100 99 100 100 100 100 100 99 100 100 1-4  250 100 100 99 100100 100 100 100 100 100 100 100 100 99 100 1-13 250 100 100 100 100 100100 80 100 100 100 100 90 50 90 65 1-15 250 100 100 100 100 100 100 100100 100 100 100 60 50 40 90 1-21 250 100 100 60 95 100 98 40 98 75 85 990 35 0 20 1-25 250 100 100 100 100 100 100 95 100 100 100 100 99 40 8585 1-26 250 100 100 99 100 100 100 99 100 100 100 100 100 98 100 98 1-27250 100 100 100 100 100 100 80 100 100 100 100 55 35 85 80 1-28 250 100100 100 100 100 98 100 100 100 100 100 85 40 75 65 1-33 250 100 100 6570 100 100 75 99 55 70 100 0 15 10 10 1-37 250 100 60 40 85 100 98 35 015 25 40 15 10 20 20 1-48 250 100 100 100 100 100 99 60 100 100 100 10070 40 55 25 1-49 250 100 100 100 100 100 100 85 100 100 100 100 70 50 7060 1-50 250 100 100 99 90 100 100 75 100 99 100 99 85 60 50 25 1-51 250100 100 100 98 100 100 99 100 100 100 100 70 65 70 60 1-52 250 100 10097 95 100 98 85 90 85 100 80 50 50 0 0 1-53 250 100 100 100 95 100 95100 99 95 90 98 25 50 5 15 1-54 250 100 100 99 75 100 95 90 98 85 99 9555 55 0 0 1-55 250 100 99 100 100 100 100 95 100 100 100 100 20 60 40 31-56 250 100 100 100 100 100 100 100 100 100 100 100 50 15 75 55 1-57250 100 100 100 100 100 100 95 100 100 100 100 50 50 65 35 1-59 250 100100 99 85 100 100 60 100 99 100 99 40 15 50 45 1-60 250 100 100 98 100100 80 85 100 100 100 100 80 40 70 50 1-61 250 100 100 65 98 100 80 60100 99 100 98 0 25 10 15 1-62 250 65 90 50 60 100 35 25 100 90 90 50 1010 50 45 1-63 250 100 100 99 100 100 100 100 100 100 100 100 100 50 10090 1-64 250 100 100 100 100 100 100 100 100 100 100 100 100 99 95 901-66 250 100 100 98 100 100 100 50 100 100 100 100 95 35 85 50 1-68 250100 99 40 40 100 65 30 100 98 99 100 5 5 0 30 1-73 250 100 100 90 100100 80 65 100 100 100 100 100 60 100 90 1-74 250 98 100 75 95 99 80 98100 98 99 99 100 95 99 98 1-75 250 50 100 65 99 100 85 85 99 100 100 100100 98 99 10 1-76 250 65 55 45 25 98 55 60 0 35 35 25 5 0 10 0 1-77 250100 100 90 100 100 100 98 100 100 99 100 100 100 99 99 1-78 250 20 10 1525 70 0 0 0 0 0 0 0 0 0 0 1-79 250 100 75 60 60 100 99 65 15 35 50 80 3040 30 30

TABLE 6 Post-emerge Herbicidal Activity Compd. Rate No. g ai/ha AMR ABTCAO IPH CHA AML XAS SEV ECC SOH DIS CORN SOY RICE WHEAT 1-1  250 100 10040 100 98 65 100 95 60 25 0 0 95 99 25 1-2  250 90 100 0 90 80 65 75 6060 20 0 10 50 70 25 1-4  250 0 100 0 90 99 80 90 60 50 15 0 0 60 75 251-13 250 100 100 100 100 100 100 100 100 99 100 55 25 100 99 25 1-15 250100 100 99 100 100 98 100 99 99 55 50 35 100 80 50 1-21 250 95 75 5 7599 75 80 50 25 0 0 10 25 55 45 1-25 250 100 100 100 100 100 99 100 10095 60 60 35 100 100 60 1-26 250 100 100 100 100 100 99 100 100 99 80 4040 100 90 60 1-27 250 100 100 100 100 100 98 100 100 100 75 60 60 100 9075 1-28 250 100 100 100 100 100 100 100 100 99 80 15 25 100 100 50 1-33250 99 100 60 98 99 70 70 95 65 65 25 25 60 95 65 1-37 250 100 100 15100 85 70 95 75 60 50 0 35 55 80 10 1-48 250 100 100 65 100 100 80 10098 95 30 50 10 65 60 0 1-49 250 100 100 100 100 100 80 100 100 100 65 9935 80 85 50 1-50 250 100 100 75 100 100 70 100 70 99 55 70 20 75 65 351-51 250 100 100 100 100 100 85 100 100 100 80 90 50 60 75 60 1-52 250100 100 50 70 100 60 75 0 50 0 0 0 0 0 0 1-53 250 100 100 50 100 100 75100 60 70 0 0 5 20 0 10 1-54 250 80 100 40 60 99 80 65 65 0 0 0 0 45 0 01-55 250 100 100 99 100 100 85 100 99 95 50 35 15 75 75 50 1-56 250 100100 100 100 100 100 100 100 100 85 100 20 100 99 30 1-57 250 100 100 100100 100 80 100 99 80 40 10 10 100 65 50 1-59 250 100 100 70 100 100 80100 99 99 65 99 10 45 55 35 1-60 250 85 100 60 100 100 70 85 95 98 0 0 550 0 30 1-61 250 75 98 30 100 99 60 90 85 35 20 0 3 25 30 30 1-62 250 9980 35 75 100 90 65 60 30 0 30 0 0 70 50 1-63 250 100 100 50 100 100 45100 100 100 99 80 20 100 75 30 1-64 250 100 100 85 100 100 95 100 100100 85 40 5 100 0 15 1-66 250 100 100 75 100 100 80 100 98 100 75 95 10100 100 30 1-68 250 100 80 0 60 100 40 60 0 0 0 0 10 10 0 0 1-73 250 3065 0 55 90 50 40 50 0 0 0 0 60 75 0 1-74 250 60 55 0 0 65 55 10 65 0 0 00 0 0 0 1-75 250 0 90 0 80 80 45 20 0 0 0 0 0 55 40 0 1-76 250 0 0 0 0 00 0 0 0 0 0 0 0 0 0 1-77 250 25 50 0 75 90 0 50 0 0 0 0 0 10 35 0 1-78250 60 0 0 75 99 70 80 0 0 0 0 0 10 60 50 1-79 250 70 75 0 60 65 80 0 6525 0 0 0 0 0 0

What is claimed is:
 1. A compound represented by the formula (I) or itssalt:

wherein Q is a heterocycle selected from the group consisting of QI toQ24:

wherein R₁ is hydrogen, alkyl, haloalkyl, alkenyl, alkynyl, amino,alkoxyalkyl, acetyl, alkoxycarbonylamino or alkoxycarbonyl; R₂ is alkyl,haloalkyl, alkoxy, haloalkoxy or unsubstituted or substituted phenyl; R₃is hydrogen, halogen, nitro, amino, alkylamino, haloalkylamino, cyano oramide; R₄ and R₅ are independently oxygen, sulfur or imino; Q6, Q7, Q10,Q16 or Q17 may be unsaturated containing one or two double bonds in the6-membered ring; Y is hydrogen or halogen; —L—X— is —CR₆R₇—O, or—CR₆R₇—S—, A is —C(O)—; A′ is —C(O)—; n is an integer of 1; m is aninteger of 1; B is N; E is —CR₁₂R₁₃,—, D is —NR—, R₆ and R₇ areindependently hydrogen or alkyl; R₁₂, and R₁₃, are independentlyhydrogen, alkyl, alkenyl, or phenyl, heteroaryloxy, where any of thesegroups may be substituted with at least one substituent selected fromthe group consisting of halogen and alkoxy; R is hydrogen, or alkyl. 2.The compound according to claim 1, wherein the formula (I) is

Wherein Q, R, R₆, R₇, R₁₂, R₁₃ and Y are the same as defined in claim 1.3. The compound according to claim 1, wherein Q is Q 1-5, Q16 or Q17. 4.The compound according to claim 1, wherein Y is fluorine.
 5. Thecompound according to claim 1, wherein the formula (I) is (I-1)

Wherein Q is Q1 or Q3; Y is fluorine; and R, R₆, R₇, R₁₂ and R₁₃ are thesame as defined in claim
 1. 6. The compound of claim 5, wherein thecompound is 8-[1-Methyl-6-(trifluoromethyl)-2,4-(1H,3H)-pyrimidinedione-3-yl]-9-fluoro-5H-pyrazino[1,2,3de]1,4-benzoxazine-3,6-(2H,7H)-dione (1-1),8-[4-Chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-9-fluoro-5H-pyrazino[1,2,3-de]-1,4-benzoxazine-3,6(2H,7H)-dione (1-13),8-[4-Chloro-5-(difluoromethoxy)-1-methyl-1H-pyrazole-3-yl)-9-fluoro-5H-pyrazino[1,2,3-del-1,4-benzoxazine-3,6(2H,7H)-dione (1-25),9-Fluoro-8-(4,5,6,7-tetrahydro-2H-isoindole-1,3-dione-2-yl)-5H-pyrazino[1,2,3de]-1,4-benzoxazine-3,6(2H,7H)-dione (1-37),8-[4-Chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-9-fluoro-2R-methyl-5H-pyrazino[1,2,3dej-1,4-benzoxazine-3,6(2H,7H)-dione(1-48),8-[4-Chloro-1-methyl-5-trifluoromethyl)-1H-pyrazol-3-yl-2,2-dimethyl-9-fluoro-5H-pyrazino[1,2,3-de]-1,4-benzoxazine-3,6(2H,7H)-dione (1-52) and8-[4-Chloro-5(difluoromethoxy)-1-methyl-IH-pyrazole-3-y)-9-fluoro-2-R-methyl-5H-pyrazino[1,2,3de]-1,4-benzoxazine-3,6(2H,7H)-dione (1-55).
 7. A herbicidal composition, characterized in that itcontains at least one compound according to claim 1 and an agriculturaladjuvant.
 8. A method for controlling undesired vegetation whichcomprises applying to a locus to be protected a herbicidally effectiveamount of a compound of claim
 1. 9. The method of claim 8 wherein thelocus to be protected is a cereal crop field.
 10. The method of claim 8wherein the compound of claim 1 is applied to soil as a preemergentherbicide.
 11. The method of claim 8 wherein the compound of claim 1 isapplied to plant foliage.
 12. A process for preparing a compoundrepresented by the formula (I′) or its salt: wherein Q is a heterocycleselected from the group consisting of Q1 to Q24:

wherein Q is a heterocycle selected from the group consisting of Q1 toQ24:

wherein R₁ is hydrogen, alkyl, haloalkyl, alkenyl, alkynyl, amino,alkoxyalkyl, acetyl, alkoxycarbonyl amino, alkylcarbonylamino oralkoxycarbonyl; R₂ is alkyl, haloalkyl, alkoxy, haloalkoxy orunsubstituted or substituted phenyl; R₃ is hydrogen, halogen, nitro,amino, alkylamino, haloalkylamino, cyan or amide; R₄ and R₅ areindependently oxygen, sulfur or imino; Q6, Q7, Q10, Q16 or Q17 may beunsaturated containing one or two double bonds in the 6-membered ring; Yis hydrogen or halogen; —L—X— is —CR₆R₇—O—, or —CR₆R₇—S—; A is —C(O)—;A′ is —C(O)—; n is an integer of 1; m is an integer of 1; B is N; E is—CR₁₂R₁₃—; D is —NR—; R₆ and R₇ are independently hydrogen or alkyl;R₁₂, and R₁₃, are independently hydrogen, alkyl, alkenyl, akenyl, orphenyl, where any of these groups may be substituted with at least onesubstituent selected from the group consisting of halogen, and alkoxy; Ris hydrogen or alkyl, which comprises of reacting a compound representedby the formula (II):

with a compound selected from the group consisting of an appropriatelysubstituted alkyl halide, alkyl acid halide, alkyl acid anhydride, arylacid anhydride, alkyhaloformate, aryl isocyanate, alkyl dihalide,aliphatic aldehyde, aliphatic ketone, aromatic aldehyde, and aromaticketone followed by cyclization.